CN107051219A - The preparation and its application of ionic liquid/graphene oxide gas separation membrane - Google Patents
The preparation and its application of ionic liquid/graphene oxide gas separation membrane Download PDFInfo
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- CN107051219A CN107051219A CN201710214168.6A CN201710214168A CN107051219A CN 107051219 A CN107051219 A CN 107051219A CN 201710214168 A CN201710214168 A CN 201710214168A CN 107051219 A CN107051219 A CN 107051219A
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- Prior art keywords
- ionic liquid
- graphene oxide
- gas separation
- separation membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a kind of preparation method and applications of ionic liquid/graphene oxide gas separation membrane.Graphene oxide is dispersed among ionic liquid, gas separation membrane is made by vacuum filtration, so that ionic liquid is limited among graphene oxide layer, using ionic liquid to the solubility of gas with various and the difference of diffusion coefficient, the efficient stable separation of gas is realized.
Description
Technical field
The present invention relates to the preparation of composite gas separation membranes and application field, and in particular to a kind of ionic liquid/oxidation
The preparation and its application of graphene gas separation membrane.
Background technology
Graphene oxide has superior mechanical performance, good chemical stability, unique two-dimensional structure and maturation
Preparation technology, multilayer graphene oxide film has nano level passage, there is huge application potential in gas separation field.But
Be pure graphene oxide film separative efficiency it is not high, generally require other materials to be modified, prepare laminated film.
Ionic liquid is excellent so that its vapour pressure is small, heat endurance is good, electrochemical window is big etc. as a kind of novel green solvent
Gesture is applied to multiple fields.In common gas, ionic liquid is to carbon dioxide compared to there is higher dissolving to other gases
Degree so that ionic liquid has the application potential of separation and carbon dioxide-enriched, but due to the characteristic of its liquid, mobility compared with
By force so that the less stable in the separation of gas and enrichment process.Ionic liquid is limited in graphene oxide sheet by the present invention
In layer, then the problem of solving stability well.
The content of the invention
The present invention is that, in order to overcome pure zirconia graphene film low separation efficiency, and pure ionic liquid continues when being used to separate
Property difference defect there is provided a kind of preparation method and applications of ionic liquid/graphene oxide gas separation membrane.
The preparation method of ionic liquid/graphene oxide gas separation membrane, comprises the following steps：By made from chemical oxidation
Graphene oxide is dispersed among ionic liquid, obtains graphene oxide/ionic liquid solution；Pass through vacuum filtration again
Ionic liquid/graphene oxide gas separation membrane is made by graphene oxide/ionic liquid solution suction filtration to substrate in method.
The technical principle of the present invention is as follows：
The obtained pure zirconia graphene film of vacuum filtration has layer structure of the interlamellar spacing below 1 nanometer；Will oxidation
Graphene dispersion is in ionic liquid so that graphene oxide layer and ionic liquid are well-bonded, passes through the side of vacuum filtration
Film is made in formula, and ionic liquid is limited among the lamella of graphene oxide；It is oxidized the ion of graphene sheet layer limitation
Liquid property can change, the ability of enhancing gas separation, and stability strengthens during gas is separated, Ke Yichang
Time is applied.The consumption of regulation ionic liquid and graphene oxide can adjust thickness and the ratio shared by ionic liquid.
Preferably, ionic liquid used be 1- butyl -3- methyl imidazolium tetrafluoroborates, wherein graphene oxide/
The mass percent concentration of graphene oxide is 0.001%~0.02% in ionic liquid solution；Negative pressure during vacuum filtration
It is not less than 50KPa；Described substrate is makrolon perforated membrane or inorganic oxide aluminium perforated membrane.
Preferably, ionic liquid used be 1- ethyl-3-methylimidazole tetrafluoroborates, wherein graphene oxide/
The mass percent concentration of graphene oxide is 0.001%~0.02% in ionic liquid solution；Negative pressure during vacuum filtration
It is not less than 50KPa；Described substrate is makrolon perforated membrane or inorganic oxide aluminium perforated membrane.
Further, the matter of the ionic liquid described in aforesaid way/graphene oxide gas separation membrane intermediate ion liquid
It is 50%~80% to measure percentage.
Ionic liquid made from any of the above-described technical scheme/graphene oxide gas separation membrane, can be used for separating dioxy
Change carbon and hydrogen, carbon dioxide and methane.In separation process, applicable pressure is 0.01MPa~0.15MPa, temperature is 20~
120℃.Either still being directly separated for mixed gas all shows excellent effect from the flux difference of pure gas.
The present invention has the advantages that：Using graphene oxide as support, ionic liquid is limited in graphite oxide
In alkene lamella, it greatly strengthen the ionic liquid under the conditions of stability, and confinement and the ability that gas is separated also added
By force so that laminated film has significant gas separating capacity.
Brief description of the drawings
Fig. 1 is surface and the profile scanning electron microscopic picture of graphene oxide film；There is obvious elongated sharp fold on surface,
Section has obvious layer structure；
Fig. 2 is the surface of [BMIM] [BF4]/graphene oxide gas separation membrane made from embodiment 1 and profile scanning electricity
Mirror picture；
Fig. 3 is the surface of [BMIM] [BF4]/graphene oxide gas separation membrane made from embodiment 2 and profile scanning electricity
Mirror picture；
Fig. 4 is the surface of [EMIM] [BF4]/graphene oxide gas separation membrane made from embodiment 3 and profile scanning electricity
Mirror picture.
Embodiment
Below in conjunction with drawings and examples, the present invention is further illustrated.
Embodiment 1
At room temperature, graphene oxide/[BMIM] [BF that configuration graphene oxide mass percent concentration is 0.016%4]
Solution, suction filtration 1ml solution is made on aperture 200nm inorganic oxide aluminium perforated membrane to diameter 25mm under 85KPa negative pressure
[BMIM] [BF thick 750nm4]/graphene oxide gas separation membrane, wherein [BMIM] [BF4] mass percent be 56%.From
It can see in the electron microscope of film surface, added [BMIM] [BF4] afterwards compared to pure zirconia graphene film, fold is
Gentle and reduction；It can see from the electron microscope of section, [BMIM] [BF4] be filled in the lamella of graphene oxide film,
Thickness has obvious increase, and interlamellar spacing is stretched, and can't see under Electronic Speculum obvious layer structure.By the seperation film in room
The flux of carbon dioxide, hydrogen and methane is measured under the conditions of temperature, 0.06MPa, carbon dioxide and hydrogen, carbon dioxide and first is obtained
The flux ratio of alkane is respectively 8 and 30.
Embodiment 2
At room temperature, graphene oxide/[BMIM] [BF that configuration graphene oxide mass percent concentration is 0.004%4]
Solution, suction filtration 4ml solution is made 1 μm to diameter 25mm under 85KPa negative pressure on aperture 200nm inorganic oxide aluminium perforated membrane
Thick [BMIM] [BF4]/graphene oxide gas separation membrane, wherein [BMIM] [BF4] mass percent be 66%.From film
It can see in the electron microscope on surface, [BMIM] [BF4] amount increase so that the fold on surface is further reduced, and is occurred
Spherical projection；It can see from the electron microscope of section, film thickness further increases.By the seperation film in room temperature,
The flux of carbon dioxide, hydrogen and methane is measured under the conditions of 0.06MPa, carbon dioxide/hydrogen and carbon dioxide/methane ratio is obtained
Value is respectively 32 and 382.Under the same conditions carbon dioxide/hydrogen mixed gas and carbon dioxide/first are measured with gas chromatograph
The separating property of alkane gaseous mixture, it is respectively 10 and 39 to obtain segregation ratio.
Embodiment 3
At room temperature, graphene oxide/[EMIM] [BF that configuration graphene oxide mass percent concentration is 0.007%4]
Solution, suction filtration 2ml solution is made on aperture 200nm inorganic oxide aluminium perforated membrane to diameter 25mm under 85KPa negative pressure
[EMIM] [BF thick 800nm4]/graphene oxide gas separation membrane, wherein [EMIM] [BF4] mass percent 58%.From thin
It can see in the electron microscope on film surface, added [EMIM] [BF4] afterwards compared to pure zirconia graphene film, fold is flat
Relax and reduce；It can see from the electron microscope of section, [EMIM] [BF4] be filled in the lamella of graphene oxide film, film
Thickness has obvious increase, and can't see under Electronic Speculum obvious layer structure.By the seperation film under the conditions of room temperature, 0.06MPa
The flux of carbon dioxide, hydrogen and methane is measured, it is respectively 9 Hes to obtain carbon dioxide/hydrogen and carbon dioxide/methane ratio
33。
Embodiment described above is a kind of preferably scheme of the present invention, and so it is not intended to limiting the invention.Have
The those of ordinary skill for closing technical field, without departing from the spirit and scope of the present invention, can also make various changes
Change and modification.Therefore the technical scheme that all modes for taking equivalent substitution or equivalent transformation are obtained, all falls within the guarantor of the present invention
In the range of shield.
Claims (7)
1. the preparation method of a kind of ionic liquid/graphene oxide gas separation membrane, it is characterised in that comprise the following steps：Will
Graphene oxide is dispersed among ionic liquid made from chemical oxidation, obtains graphene oxide/ionic liquid solution；Again
By the method for vacuum filtration by graphene oxide/ionic liquid solution suction filtration to substrate, ionic liquid/graphite oxide is made
Alkene gas separation membrane.
2. preparation method according to claim 1, it is characterised in that ionic liquid used is 1- butyl -3- methyl miaows
The mass percent concentration of graphene oxide is 0.001% in azoles tetrafluoroborate, wherein graphene oxide/ionic liquid solution
~0.02%；Negative pressure is not less than 50KPa during vacuum filtration；Described substrate is makrolon perforated membrane or inorganic oxide
On aluminium perforated membrane.
3. preparation method according to claim 1, it is characterised in that ionic liquid used is 1- ethyl -3- methyl miaows
The mass percent concentration of graphene oxide is 0.001% in azoles tetrafluoroborate, wherein graphene oxide/ionic liquid solution
~0.02%；Negative pressure is not less than 50KPa during vacuum filtration；Described substrate is makrolon perforated membrane or inorganic oxide
On aluminium perforated membrane.
4. the preparation method according to Claims 2 or 3, it is characterised in that described ionic liquid/graphene oxide gas
The mass percent of seperation film intermediate ion liquid is 50%~80%.
5. ionic liquid/graphene oxide gas separation membrane according to made from Claims 1 to 4 any preparation method.
6. the application of ionic liquid/graphene oxide gas separation membrane according to claim 5, it is characterised in that obtained
Ionic liquid/graphene oxide gas separation membrane is used to separate carbon dioxide and hydrogen, carbon dioxide and methane.
7. application according to claim 6, it is characterised in that in separation process, applicable pressure for 0.01MPa~
0.15MPa, temperature is 20~120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710214168.6A CN107051219B (en) | 2017-04-01 | 2017-04-01 | Preparation and application of ionic liquid/graphene oxide gas separation membrane |
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| CN201710214168.6A CN107051219B (en) | 2017-04-01 | 2017-04-01 | Preparation and application of ionic liquid/graphene oxide gas separation membrane |
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| CN107051219A true CN107051219A (en) | 2017-08-18 |
| CN107051219B CN107051219B (en) | 2020-07-07 |
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| CN201710214168.6A Expired - Fee Related CN107051219B (en) | 2017-04-01 | 2017-04-01 | Preparation and application of ionic liquid/graphene oxide gas separation membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646613A (en) * | 2019-10-12 | 2021-04-13 | 中石化南京化工研究院有限公司 | Absorbent and method for separating and recovering carbon dioxide in blast furnace gas |
Citations (3)
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|---|---|---|---|---|
| CN102533406A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Graphene-containing ionic liquid nanometer composite lubricating membrane |
| CN103971943A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor |
| CN105502350A (en) * | 2015-11-29 | 2016-04-20 | 南京新月材料科技有限公司 | Graphene oxide and ionic liquid composite film and preparation method thereof |
-
2017
- 2017-04-01 CN CN201710214168.6A patent/CN107051219B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533406A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Graphene-containing ionic liquid nanometer composite lubricating membrane |
| CN103971943A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor |
| CN105502350A (en) * | 2015-11-29 | 2016-04-20 | 南京新月材料科技有限公司 | Graphene oxide and ionic liquid composite film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 姜海超: "离子液体性质及其与SO2相互作用机理研究", 《中国博士学位论文全文数据库（工程科技I辑）》 * |
| 赵薇等: "离子液体二氧化碳分离膜研究进展", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646613A (en) * | 2019-10-12 | 2021-04-13 | 中石化南京化工研究院有限公司 | Absorbent and method for separating and recovering carbon dioxide in blast furnace gas |
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| CN107051219B (en) | 2020-07-07 |
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